Rhodamine dyes



Patented Feb. 19, 1935 RHODAMINE DYES v Otto Allemann, Wilmington, DeL, assignor I., i

du Pont de Nemours & Company; Wilmington, I Del., a corporation of Delaware.

No Drawing Application March 24, 1932 Serial N0. 601,061

12 Claims. (algae- 63) This invention relates to rhodamine dyes and more particularly to halogenated rhodamine dyes. The object of this invention is the production of halogenated rhodamine dyestuffs. Further objects are the production of rhodamine dyestuffs capableof dyeing silks and wool in fast brilliant shades ranging from red to violet; and'the production of halogenated rhodamine dyestuffs soluble in dilute alkaline solution. Additional objects will appear hereinafter. V

These objects are attained by the process of the present invention whereby a halogenated arylmeta-amido-phenol of the benzene series is condensed with phthalic anhydride and the condensation product sulfonated. These objects may also be attained by condensing a halogenated primary amine of the benzene series with fluorescein dichloride and sulfonating the "subsequent condensation product.

This invention may be more completely understood by a consideration of the following examples wherein the parts given are all byweight:

Example I T 1 I Y Part5 Fluorescein dichloride 8 G-chlor-o-toluidine (1CH3, 2NH2, 6C1) Anhydrous zinc chloride 2 Zinc oxide 2 EmampZeII Parts Phthalic anhydride 40 6-chlor-o-tolyl-meta-amido-phenol Anhydrous zinc chloride 12 were slowly heated up to 200 C; and this temperature maintained until the fusion became thick. The cold fusion mass was ground to a fine powder and extracted with hotdilute caustic soda solution. The residue was filtered off, washed and driedij The. sulfonation'wajs carried out in th sameway as given under Example I, 1 I p Example III Fluorescein dichloride 12 5-'chlor-o-toluidine -25 Anhydrous zinc-chloride 3 Zinc oxide 3 were heated to 210-220? C. until the melt became thick. When cold the masswas ground to a fine powder, extracted with "boiling dilute hydrochlo ric acid, filtered, washed and dried. 1' The sulfonation was carried out inthe same Example-I. I H p v Fluoresceinoichloride 12 o-chloranilineu l -I 2Q Anhydrous zinc chlorides; 3

Zinc oxide"--- 3 Grams Fluorescein dichloride 8 p-bromaniline 15 Anhydrous zinc 011.101.16.84; 2 Zing oxide 1 2 were heated to 210-220? C. until the fusion mass became hard. When cold the mass was finely ground, extracted with hot dilute hydrochloric acid, filtered, washed and dried. It was then sulfonated in the usual way.

In place of the halogenated primary amine of the benzene series, mentioned in the above examples, it is possible to substitute any other halogenated primary amine of the benzene series with comparable results. Very satisfactory results may also be obtained by substituting any other halogenated aryl-meta-amido-phenol v of the benzene series for fi-chlor-o tolyl-meta-amido-phenol, mentioned in Example II.

Grams way as under The rhodami'nes produced by the process of this invention have the following general formula:

in which R and R are 'haloge'natedmembers of the benzene series which may have substituted thereon members of the alkyl group, and in which R also has substituted thereon a sulfonic acid group.

textile manufacturers and commercial dyeing establishments. attractive but are extremely fast to washing, and

retain their original brilliance afte repeate (r washings. The shades range from red to violet, according to the compounds used, and provide a in the appended claims.

' claima .1 A. rocess .9 odu n rh d n dyes w ich. com rises con ens g. a a te r amine or heben ene ssrieswi h .flmres e n dichloride and sulfonating thecondensed product. 2, -A process of producing rhodamine dyes which comprises condensingfa halogenated toluidine with fiuoresceinjdichloride and sulfonating the condensed. product,-

3. A process of producing rhodamine dyes which comprises condensing a halogenated-ot-oluidine with fiuorescein dichloride and sulfonating the condensed product.

4 .-A- process of producing 'rhodamine dyes which comprises condensing -6.-ch1or--otoluidine with 'fiuoresceindiehloride' and sulfonating' the condensed product. I i

bQqompounds Whose formula is:

in which Rand R represent the residues of ha1o= These shades are not omy'wery genated primary amines of the benzene series, 7 i

and in which R also contains a sulfonicacid group.

3 soul;

11 K i i; i

coonwherein X represents hydrogen or an .alkyl 1 a -group, and Y- represents a halogen group.

' The products of the present invention produce brilliant shades which are ingreatdemandZbY 7. Dyes having the following general formula:

' SOaNa H l "8. Compounds whose formula is:v

6. Dyes having the following general formula:

* U -iI- o'r'ro ALLEMANN.

color 'is due 

